DE2802234A1 - PAINT FORMATION INHIBITING DISPERSION AGENTS FOR LUBRICATING OILS - Google Patents

Description

DR. BERG DiPL.-lNü. STAPF DIPL.-ING. SCHWABE DR. DR. SANDMAIR

PATENTANWÄLTE PO Box 860245 8000 Munich 86

Dr. Berg Dipl.-Ing. SUpf and Partner, P.O.Box 860245, 8000 Munich 86 ' Your reference Our reference Mauerkircherstraße Your ref. Our ref. 8000 MUNICH

Attorney's file 28 714 ¹ S- ^{January 1978}

Be / Ro

Exxon Research, and Engineering Company, Linden, New Jersey / USA

"Lacquer Formation-Inhibiting Dispersants for

Lubricating oils "

The present invention relates to hydrocarbon-soluble borated derivatives of oxazolines, processes for their Production and use of the borated oxazolines to improve the sludge dispersibility and / or the Paint formation-inhibiting properties of lubricating oils that are used for the engine lubrication of internal combustion engines.

809831 / 0S88

Bank accounts: Hypo-Bank Munich 4410122850 (BLZ 70020011) Swift Code: HYPO DE MM Bayer. Vereinsbank Munich 453100 (BLZ 70020270) Post check Munich 65343-808 (BLZ 70010080)

»(089) 988272 Telegrams: M 8273 BERGSTAPF PATENT Munich 988274 TELEX: 983310 0524560 BERG d

be det.

Two main cases occur with lubricants for engine lubrication on, that is, cyclically high and low temperatures during stop and go operation and continuously high temperatures during prolonged use of the vehicle over long distances. Each of these cases works in deai lubricant the presence of varying proportions of foreign particles, such as dirt, soot, water and degradation products resulting from the breakdown originate from the oil. These foreign materials appear to be responsible for the deposition of a mayonnaise-like sludge that along with the oil circulating to be responsible.

In addition to the formation of sludge, internal surfaces tend to form a deposit of paint, which results from the work of the machine continuously high temperatures results. In such a case, the breakdown of the oil leads to the formation of acidic ones Materials that as such corrode both the metal surfaces of the bearings, pistons, etc., as well as the decay of the Catalyze lubricating oil, and this breakdown manifests itself in hard, carbon-containing deposits that form in the piston ring grooves collect and form a varnish on the piston slideway skirt and bottoms and other metal surfaces.

For the past decade, ash-free sludge dispersants have been used increasing importance primarily because they improve the behavior of the lubricants, that they keep the machine free from deposits, and longer

009831/088 »

-Tr-

enable oil change of the engine lubricating oil, whereby the undesirable environmental nuisance caused by the previously used metal-containing additives can be avoided. The most of Commercially available ashless dispersants fall into several general groups. For a group there is a Amine or polyamine combined with a long-chain hydrocarbon polymer (the oil-solubilizing part of the molecule), usually polyisobutylene through an acidic group, such as a monocarboxylic acid material as described, for example, in US Pat. No. 3,444,170, or a dicarboxylic acid material such as polyisobutenyl succinic anhydride, to form amide or imide compounds, as in the US patents 3,172,892 and 3,272,746 and this group of commercially available dispersants can be the reaction product such materials with boron (see U.S. Patents 3,087,936 and 3,254,025, which generally include form a mixed boric acid salt which is quite unstable hydrolytically, thereby reducing its usefulness will.

The reaction products of acylated nitrogen intermediates (from the reaction of an alkenyl succinic acid forming compound and a hydroxy hydrocarbon amine) and a Boron compounds are also contemplated as additives for lubricants in US Pat. No. 3,282,955, but they were not yet commercially successful, probably because of their inadequate sludge dispersing effectiveness.

$ 09831/058 »

The reaction products of hydrocarbyl-substituted succinic anhydride, for example polyisobutenylsuccinic anhydride, are compounds containing both an amine and a hydroxyl group have been contemplated or studied in the prior art. For example, British Patent 809,001 describes corrosion inhibitors containing a multiple salt complex formed from the reaction product of hydrocarbon-substituted dicarboxylic acids and hydroxyamines (including 2-amino-2-methyl-1,3-propanediol) / MSj and tris- (hydroxymethyl) aminomethane / TRIM / descends. Furthermore, British Patent 984,409 describes ashless lubricant additives of the amide / 3jnide / ester type which are prepared by reacting an alkenyl succinic anhydride, the alkenyl group having from 30 to 700 carbon atoms, with a hydroxyamine including THAM. In contrast, German patent specification (DOS) 2512201 teaches that by reacting a hydrocarbon dicarboxylic acid material, ie the acid, the anhydride or the ester, with certain types of amino alcohols, under certain conditions including the conveyance of metal salts, products can be obtained which have one or more have two heterocyclic bings, namely an oxazoline ring, and that products containing at least one oxazoline ring can be provided for various functions such as anti-rust agents, detergents or dispersants for oil-containing preparations including lubricating oil, gasoline, turbine oils and oils for drilling purposes.

809831/065 »

In none of the foregoing references is there any suggestion that the reaction products may advantageously be borated could be.

In contrast to the teachings of the prior art about lubricating oil additives, mono-oxazolines have been expediently used for Use as a gasoline additive borated to eliminate the adverse effects of combustion deposits in the engine, to suppress surface (glow ignition) and carburetor icing (see U.S. Patents 2,948,597, 2,965,459, 2 993 765, 3 030 374, 3 030 375, 3 070 603). Such gasoline additives are not suitable for lubricating oils because they have a it lacks satisfactory sludge dispersing effectiveness and there is no evidence that it can inhibit the acid-induced catalytic degradation of lubricating oils could be "

Products of the dicarboxylic acid lactone type have so far also been envisaged because of their anti-rust and / or dispersing properties, which you can give them by reacting with hydroxyamines, such as Ethanolamine and diethanolamine (see U.S. Patents 3,248,187 and 3,620,977).

It has now been found that a hydrolytically stable borated oxazoline lubricating oil additive with unexpectedly improved Paint formation inhibition effectiveness can be obtained by using a boron compound, for example boric acid, with the hydroxyalkyl groups of the oxazoline ring of an oil solution

809831/0881

condensed hydrocarbon-substituted oxazoline material, with about 0.1 to 2.0, preferably 0.3 to 1.0, weight percent boron being present as the borate ester in this material.

Although the boron can sometimes be introduced more easily at temperatures up to about 20O ⁰ C by transesterification of this oxazoline material, an undesirable increase in viscosity and gel formation can occur. In addition, the introduction of boron via an acidic compound such as boric acid at such high temperatures can convert the oxazoline material into indefinable mixtures of boron-containing imide / amide products with reduced sludge dispersion and / or lacquer inhibiting effectiveness by destroying the oxazoline ring.

It has now further been found that boric acid, if any, occurring destruction of the oxazoline ring can be used with less when effecting the esterification at a temperature not higher than 120 ⁰ C, preferably in the range of about 60 to 100 ⁰ C. , thereby maintaining the improved dispersion activity obtained from the presence of the intact boron-containing oxazoline ring structure.

The present invention accordingly provides a lubricating oil preparation, which is a major amount of lubricating oil and a smaller, but dispersing amount, a dispersing and lacquer-inhibiting one Oil-soluble boron-containing oxazoline material, which contains about 0.1 to 2.0 wt. # boron and

809831/068 *

is further characterized in that there are one to two oxazoline rings and contains substantially saturated hydrocarbon groups of at least about 50 carbon atoms.

The various types of preferred borated oxazoline materials can be represented by the following structural formulas;

(A) Borated hydrocarbon-substituted mono-oxazoline

CH ₂ O

/ C. B-OX

C j CH ₂ O

H ^X \ CH ₂
RC \ / ²

0 - Z

(B) Borated hydrocarbon-substituted bis-oxazoline

CH ₉ O

^X C B-OX

R - C ^X \

H ₂ C

809831 / 068S

Borated hydrocarbon lactone oxazoline

C-O

HC

H ₂ C

'CH ₂ O _x

BOX

where in all preceding Pormeha E the oil-solubilizing Hydrocarbon substituents, preferably an alkenyl substituent represents, with an (SL) of about 700 to 140,000 (alternatively with about 50 to 10,000 carbon atoms), preferably 900 to 20,000, and best possible about 1200 to 5,000, X hydrogen, a hydrocarbon ^ preferably Alkyl) or a heterocarbyl group having 4 to 20 carbon atoms, where, when X is hydrogen, the corresponding cyclic and acyclic boron anhydrides of this oxazoline-in fall within the scope of the preferred borated oxazoline materials, Y hydrogen, hydroxyl, sulfο, alkylthio (RS-), alkyldithio- (ESS-) and / or a sulfur bridge, for example -S- and -S-S-, which is the two lactonoxazoline units connects with each other and Z is a suitable inner ester bond with a hydroxyalkyl group is this oxazoline ring, T being defined later.

Bas hydrocarbon-substituted dicarboxylic acid material, i.e. the acid or the anhydride or the ester used to produce

009831 / oeet ■ *

position of the dispersants and / or the paint formation inhibitors used is made from alpha-beta unsaturated C.- to CjQ-dicarboxylic acids or their anhydrides or esters, such as fumaric acid, itaconic acid, maleic acid, maleic anhydride, chloromaleic acid, dimethyl fumarate, etc. are produced. These acidic materials are with a hydrocarbon group, preferably a hydrocarbon chain with at least 50 Carbon atoms (branched or unbranched), substituted.

Generally these are hydrocarbon-substituted Dicarboxylic acid materials and their preparation are known to those skilled in the art, see for example US Patents 3,219,666, 3 172 892, 3 272 746, also the aforementioned patents, and they are commercially available, for example polyisobutylene succinic anhydride.

The dicarboxylic acid material can be substituted by an alkenyl Anhydride are explained, which contains a single alkenyl radical or a mixture of alkenyl radicals in different Manner are linked to the cyclic succinic anhydride group, it being understood that the following structures can be present

I ^E 1 T

^N c σ

c 2 * ^GE

v_

D I

It

809831/0681

RH ₂ G

- ie -

wherein E is hydrogen or a lower _{hydrocarbon group and R 1 is} a hydrocarbon or substituted hydrocarbon group having from 50 "to about 10,000 and more carbon atoms, and preferably from 60 to about 300 carbon atoms. The anhydrides can be obtained by well-known methods, such as by the Ene reaction between an olefin and maleic anhydride or halosuccinic anhydride or succinic ester (US Pat. No. 2,568,876). In the branched olefins, especially the branched polyolefins, R can be hydrogen or methyl and R 1 can be a long chain hydrocarbon group having at least 50 carbon atoms. The exact structure cannot always be determined and the various R and R -.- groups cannot always be precisely defined in the Ene products of polyolefins and maleic anhydride.

Suitable olefins include butene, isobutene, pentene, decene, dodecene, tetradecene, hexadecene, octadecene, eicosene and polymers of propylene, butene, isobutene, pentene, decene and the like, and halogen-containing olefins. The olefins can also Contain cycloalkyl and aromatic groups.

With 2-chloromaleic anhydride and related acylating agents alkenyl maleic anhydride reactants are formed. The formation of derivatives of these reactants also provides useful oxazoline products «

The preferred olefin polymers for reaction with the un-

809831/068 «

Saturated dicarboxylic acids are polymers which contain a major molar amount of C ₂ to C ^ monoolefin, for example ethylene, propylene, butylene, isobutylene and pentene. The polymers can be both homopolymers such as polyisobutylene and copolymers of two or more such olefins such as copolymers of ethylene and propylene, butylene and isobutylene, propylene and isobutylene, and so on. Other copolymers include those in which a smaller amount of the copolymer monomers, for example 1 to 20 mol $, a G.- to O-ig non-conjugated diolefin, or a copolymer of ethylene, propylene and 1,4-hexadiene, etc. is.

The olefin polymers usually have a number average molecular weight (M _Q ) in the range from about 700 to about 140,000, more usually between about 900 to about 10,000. Particularly useful olefin polymers have (M _n ) values of about 1200 to 5,000 with approximately one terminal double bond per polymer chain. A particularly valuable starting material for a particularly effective dispersion additive are polyalkenes, for example polyisobutylene, with about 90 carbon atoms.

In general, useful oil-soluble oxazoline reaction products are and processes for their preparation are described in detail in German patent specification DOS 2512201. These oxazoline dispersants, which form part of the combination according to the invention can in their preferred form as a

809831/0661

öllösliclies product are characterized, which is obtained in that one molar equivalent of a hydrocarbon-substituted ⁰ AG-Io saturated dicarboxylic acid material with more than about 50 carbon atoms per dicarbonacyl group with 1 to 2, preferably 1.5 to about 2, molar equivalents of a 2.2- disubstituted 2-amino-1-alkanol with 2 to 5 hydroxyl groups and a total content of 4 to 8 carbon atoms at a temperature of about 14-0 to 240 ⁰ O is heated together until the formation of water ceases, whereby one recognizes the termination of the oxazoline reaction. This specified amino-alkanol, with which one can easily obtain the oxazoline rings required for this dispersant according to this invention, can be represented by the general formula,

NH _Q "G- 0H ₀ OH, X

wherein X is an alkyl or hydroxyalkyl group, where at least one of the X substituents is a hydroxyalkyl group of the formula - (OHg) _n OH, where η is 1 to 3.

Examples of such 2,2-disubstituted aminoalkanols include 2-amino-2-methyl-1,3-propanediol, 2-amino-2- (hydroxymethyl) -1,3-propanediol (also known as tris (hydroxymethyl) aminomethane or THASI), 2-amino-2-ethyl-1,3-propanediol, etc. THAH is particularly preferred because of its efficiency, availability and cost. It should be noted that other amino alcohols such as ethanolamine, propanolamine and butanol

809831/0681

amines lacking 2,2-disubstitution, the oxazoline product do not deliver. The required products have already been specified.

product not deliver. The required (I _n ) -areas-

The formation of the preferred oxazoline dispersants in high yield can be accomplished by adding about 1.0 (to obtain the monooxazoline) to about 2 (to obtain the bis-oxazoline) molar equivalents of the aforesaid 2,2-disubstituted-2-amino-1 -alkanols per molar equivalent of dicarboxylic acid material, with or without an inert diluent, is added and the mixture is heated at 140 to 24O ⁰ O, preferably 160 to 205 ⁰ O, in particular ^{170-190 0} O 1/2 to 24, in particular 2 to 8 hours the reaction has expired.

Completion of the oxazoline reaction can easily be determined by periodically performing infrared spectral analyzes carried out to follow the oxazoline formation (the oxazoline peak forms at 6.0 / µm) or that 'the water formation of about 1.5 to 5 »0 mol of water stops.

Although not necessary, the presence of minor amounts such as 0.01 to 2 wt on the G-ewioht of the reactants, a metal salt in the reaction mixture can be used as a catalyst. Of the Metal catalyst can then later be filtered through or by washing a hydrocarbon solution of the product with a low alcohol, such as methanol, ethanol, isopropanol, or an alcohol / barrel solution can be removed.

809831/0681

-K-

However, the metal salt may be left in the reaction mixture if it is found to be stably dispersed or dissolved in the reaction product, and depending on the metal it can contribute to the behavioral advantages of the lubricating oil. It is believed that this would be the case when using zinc catalysts in lubricants the pail is.

To inert solvents used in the oxazoline reaction include hydrocarbon oils, for example mineral lubricating oils, kerosene, neutral mineral oils, xylene, halogenated hydrocarbons, for example carbon tetrachloride, dichlorobenzene, tetrahydrofuran, etc.

Metal salts that can be used as promoters or catalysts include carboxylic acid salts of Zn, Co, Mn, Ni and Fe. Metal catalysts derived from strong acids (HCl, sulfonic acids, H ₂ SO., HNO ,, etc.) and bases tend to reduce the yield of oxazoline products and instead favor imide or ester formation. For these reasons, the strong acid or basic salts are not preferred and are usually avoided. The carboxylic acids which are used to produce the desired promoters include the C - to 0-137, for example C - to Cg acids, such as the saturated or unsaturated mono- or dicarboxylic aliphatic hydrocarbon acids, in particular fatty acids. Specific examples of such desired carboxylic acid salts include zinc acetate, zinc formate, zinc propionate, zinc stearate, manganese acetate (Manganese II acetate), iron tartrate, cobalt acetate

809831/0888

(Cobalt II acetate), nickel acetate, etc. zinc salts such as zinc acetate and zinc oxide are preferred. The metal salts include the oxides.

It is preferred that the metal salt promoter be present at or near the start of the reaction for the greatest effect to achieve. The zinc salt promoter is gradually dissolved, thereby forming zinc complexes with the oxazoline product, among other things will. The presence of zinc in the oxazoline product appears to add significant and unexpected performance benefits of the lubricating oil.

Although not known with complete certainty, it is believed that the reaction of the hydrocarbon-substituted Dicarboxylic acid material, e.g., a substituted succinic anhydride with the amino alcohol of the invention, for example about 1.5 to 2 equivalents of 2,2-disubstituted-2-amino-methanol such as tris-hydroxymethylaminomethane (THAM), oxazoline provides, for example a mixture of monooxazoline and bis-oxazoline to total bis-oxazoline through those in between various discrete reaction products. When an acid anhydride is used, the initial reaction appears to consist in that the anhydride through the hydroxyl group of one mole of the amino alcohols to form a hemiester is split. It is believed that the addition of an additional mole of amino alcohol results in a carbamic acid-like amine salt which, upon further heating, is then used Cyclodehydration to the bis-oxazoline end product under-

809831/0681

lies. The promoting effect of the metal salts, such as zinc acetate (ZnAc ₂ ), on oxazoline formation can easily be ascribed to the favorable polarization of the amide group by the zinc salt, whereby the attack by the hydroxy function of the amino alcohol reactant is facilitated. It is believed that the dissolved zinc salt will eventually coordinate with the oxazoline ring.

The oil-soluble lactone oxazoliru materials that are the subject of Vioinal lactone and oxazoline ring systems are described in detail in German patent application P 27405352. These Materials can be represented by the general formula

R X

«Ir r λ . Λττ

- OHR ^ C C-CH ₉ X \ s' ^ s. f \ ^z

OH-CH ₂ ^ "^ Jj ^N CH ₉ X,

O ^.

wherein R is a hydrogen atom and / or alkyl radicals having 1 to 400 or more carbon atoms, X is an alkyl or hydroxyalkyl radical, and at least one of the substituents X and preferably both X substituents is a hydroxyalkyl group of the general formula - (CH ₂ ) _n OH , where η = 1 to 3 and Y is hydrogen, hydroxyl, sulfo, alkylthio (TS-), alkyldithio (TSS-) and / or a sulfur bridge, for example -S- and SS-, that connects the two lactonoxazoline units

809831/0689 *

- ντ -

connects, as shown below, and in which
ζ is a number from 1 to 4 and I, as defined below, contains 1 to 50, preferably 2 to 20 carbon atoms.

CH ₉ X

A polyisobutyllactone oxazoline with a number average molecular weight of about 800 to is preferred here
100,000, for the production of which equimolar proportions of
Polyisobutyllactonecarboxylic acid with tris- ^ ydroxymethyjLjLj-aminomethane at a temperature of about 100 to 240 ⁰ C, preferably 150 to 180 ⁰ C, until 1 mole of H ₂ O per mole of reactant is removed from the reaction.

hydrocarbon-soluble compounds have at least 50 carbon atoms in the substantially saturated aliphatic hydrocarbon group and one carboxylic acid group of the dicarboxylic acid material contained in the lactone ring and

809831/068 «

another carboxylic acid group included in the oxazoline ring than Result of the reaction of at least equimolar amounts of the hydrocarbon-substituted dicarboxylic acid lactone material and a 2,2-disubstituted 2-amino-1-alkanol having 1 to 3 hydroxyl groups and a total content of 4 "to 8 carbon atoms is transferred.

As indicated, these precursor alkyl lactone oxazolines of the present invention can be prepared by one alkyl lactonic acids, esters or amides with a 2,2-disubstituted-2-amino-1 -alcohol, such as tris- (Hydroxylmethylami.nomethan, converts, as shown in the following equation is:

RY CH2OH NH ₂ C-CH20H RY

CH 0 OH ₂ OH CH O-: CH ₂ -CHR CQ ^ V-CHR ί y

c c

■ ■ · IT

ο ο

The manufacture of these alkyl lactone reactants consists of in that one uses the designated hydrocarbon-substituted dicarboxylic acid material, generally an alkenyl succinic acid analog, lactonized, this being done via the Ene reaction of an olefin with an alpha-beta-unsaturated C.- to C-iq-dicarboxylic acid or their anhydrides or esters, such as fumaric acid,

809831/0688 original wsfs = ct _ED

Itaconic acid, maleic acid, maleic anhydride, dimethyl fumarate, etc. received.

The unsubstituted or simple lactone reactants (X = H) are readily obtained by the acid catalyzed lactonization of an alkenyl dicarboxylic acid analog performs, the latter deriving from the ring cleavage of an alkenylsuccinic anhydride with water, an alcohol or an amine as shown below, wherein HQ is water, alcohols of 1 to 10 carbon atoms, and dialkylamines having 2 to 10 carbon atoms, and R has the meaning defined above.

C. H R.
f O R.
V Q R R.
I. O CH ₂ R C.
Il
O R. I. CH Il C. > / * '- Il \ l HC C. I. C. C-0 / \ / _v HC \ / \ R. HC ^N H / OH. HC C I O -s S / / N / ¹² V HC / ^Q I. I. C.
B. ^ H- ", H ₂ C
N H ₂ C ^

It is believed that the reaction with HQ opens the anhydride at the least crowded carbonyl group and forms a succinic acid hemiester or an amino acid product, which in the presence of an acidic catalyst mainly cyclizes to the 5-ring lactone product as shown above.

It is possible to have alkenyl substituents with the double bond in the 1-, 2- or 3-position or even with further double

809831/0688 CRiSJNAL Inspected

Use bonds on the hydrocarbon chain if the acidic catalyst is able to move it into a position suitable for formation of iactone. In general The size of the aceton ring formed will depend, among other things, on the position of the double bond and which carboxylic acid group participates in the lactone formation reaction. As a result, both 5- and 6-ring (or larger ring) lactones occur, as explained below:

R ^ R R-i O R ^

CH2C-Q II

Ii

For convenience, the products of the present invention are commonly presented as 5-ring lactones, although larger ring lactones may also be present.

I) Ie intramolecular ones contemplated in the method of this invention The cyclization step must be carried out in the presence of an acidic catalyst in order to ensure the formation of the lactone to effect. Suitable catalysts include the mineral acids such as hydrochloric acid, sulfuric acid, perchloric acid and phosphoric acid, the sulfonic acids such as the alkanesulfonic acids and the arylsulfonic acids, the acids of the Lewis type such as aluminum chloride, Boron trifluoride, antimony trichloride and titanium tetrachloride, Ion exchange resins of the sulfonic acid type with low

8 0 9 8 3 1/0 6 8 8 _s . "*""'**'' ^{ihsPE £ r} ^

rem molecular weight, such as crosslinked sulfonated polystyrene, which is commercially available as Dowex-50. The alkanesulfonic acid catalysts are preferably lower alkanesulfonic acids having 1 to 12 carbon atoms, for example methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid and butanesulfonic acid. If desired, a mixture of lower alkane sulfonic acids can be used, and such a mixture containing methane, ethane and propane sulfonic acids is commercially available. Usually, the Alkansulf oic acid is 92-95 fo SuIfonsäure containing 1 to 2 $ sulfuric acid and 3 to 6 $ water. The aryl sulfonic acid catalysts useful in the process of this invention include the benzenesulfonic acids, toluenesulfonic acids, and chlorobenzenesulfonic acids, with p-toluenesulfonic acid and 4-chlorobenzenesulfonic acid being preferred. The amount of catalyst present in the reaction zone can be varied over wide ranges, depending on the nature of the reactants and the catalyst used. The amount of catalyst used is also determined to a considerable extent by the temperature selected to carry out the reaction. Thus, at higher temperatures, the amount of catalyst required in the reaction is less than when lower temperatures are used, and the use of excessive amounts of catalyst at higher temperatures can promote the formation of undesirable by-products. Usually the catalyst is used in an amount between about 0.1 and 10 weight percent based on the amount of the alkenyl succinic anhydride reactant.

609831/0688

The presence of certain heteroatoms adjacent to the novel lactonoxazoline ring combination often gives this new lactonoxazoline system further desirable properties, such as the antioxidant and anti-corrosion effectiveness. In the present invention, new ways were found, hydroxyl, thiyl, sulfide, sulfoxide, sulfon and sulfo groups, to be introduced adjacent to the lactonoxazoline functions as described below:

The lactone reactants containing hydroxyl groups become prepared in such a way that peracids, hydrocarbon peroxides or aqueous hydrogen peroxide to the alkenyl succinic acid hemiester or amide, as shown below:

E H

I \

OH H OHOH

HC

⁰ p

C 0 /

H ₉ CQ ^H 2 ^C -v.

C it

it

O O

where Q has the previously defined meaning and R "hydrogen, is an acyl group having 2 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms. It can but also through the epoxidation of alkenylsuccinic acid

809831/0681

- 25 -

anlaydrid, with peracids epoxy anhydrides are obtained, which you then with (1) water, AlMiolen or amines with formation the desired hydroxy-substituted lactone reactants or (2) directly with THAM to form the lactone oxazoline end products can implement.

The thiyl-substituted lactones can expediently can be prepared via (1) the thiol-induced cleavage of the epoxy ring in epoxy anhydrides as shown below, wherein T alkyl, aryl, or heterocyclic groups of 1 to 50 Represents carbon atoms

E 33

C- ₀ H_

HC C

\ / V HC

N tsh /

hc N tsh v / \

I ο ' κ hc

H ₉ C / I

^ C / ^H 2 ^C \ _C

■ 2 ⁰ ο

or via (2) sulfonyl halide addition to the double bond in the alkenylsuccinic acids or esters with subsequent lactonization via an internal displacement of the halide, as shown below:

809831/0681

R RT CH R CH S

HC OH _{> H} \

H ₀ CQ

η ^Ü 2 ^Ü 'C

⁰ p

where T has the meaning defined above.

The type of thiyl substituted lactone product will depend of (1) the nature of the epoxide cleavage by the thiol reactant and (2) the manner of adding the sulfonyl chloride to the double bond in the alkeny, succinic acid, ester or amide reactants.

With sulfur _{halides (S x} Cl ₂ , where x1 is -4), thio-, dithio- and polythio-bis-lactones are formed. The subsequent reaction of the latter with THAM gives the corresponding thio-bis-lactonoxazolines.

By oxidizing the mono-thio-bis-lactones with peroxides both sulfoxides and sulfones are obtained. In the case of the dithio-bis-lactones, the oxidation yields sulfo-containing groups Lactones.

In another method, thiyl lactones can also be obtained by using the sulfonyl chloride reagent to the alkenyl succinic anhydride. The lactonizing

809831/0681

tion of the adduct can then be brought about that one either (1) the sulfonyl chloride adduct as such, or (2) Reacts the dehydrohalogenated Iddukt with an alcohol, water or amine. The lactonization of the dehydrohalogenated thiyl-substituted anhydride via route (2) is preferably carried out in the presence of an acidic catalyst.

Examples of thiols that are useful in making thiyl lactones via epoxide cleavage include the alkyl and aryl thiols and heterocyclic thiols such as 2-mercapto-benzothiazole. Hithiophosphoric acids, for example (RO) ₂ PC = S) -SH, are also suitable for the production of the phosphorus-containing products. In another method of preparation, the sulfonyl chloride analogs of the thiols described above can be added to the alkenyl succinic acid analogs to provide the desired thiyl-substituted lactone reactants.

According to a further embodiment of the present invention, the reaction provides the chlorosulfonic acid or its Equivalents, e.g. SO, and its complexes, with alkenyl succinic anhydrides Adducts which, after hydration, yield suIfolactonic acids. By treating the latter with TM one can obtain sulfolactone oxazoline end products under suitable conditions, the reaction partners remaining intact and only the lactonoxazoline products are formed

809831/0681

The Laktonoxazolinmaterialxen is obtained in a very high yield if at least about 1 molar equivalent of the aforementioned 2,2-disubstituted-2-amino-1-alkanol per molar equivalent of polyalkyllactonic acid, ester or amide with or without an inert diluent is added and the mixture , preferably at 100 to 240 ⁰ C 170 - 220 ⁰ C heated, until the reaction is complete, which can be determined by infrared analysis of the product with maximum absorption for oxazoline.

Although not required, the presence of small amounts, such as from 0.01 to 2 wt. $, Preferably 0.1 to 1 wt. based on the weight of the reactants, a metal salt can be used as a catalyst in the reaction mixture. The metal catalyst can later be added by filtration or by washing the product with a hydrocarbon solution a lower alcohol such as methanol, ethanol, isopropanol, etc. or with an alcohol / water solution.

The metal salt can also be left in the reaction mixture as long as it is stably dispersed in the reaction product or appears to be dissolved, and depending on the metal it may even be give behavioral advantages to oil or gasoline. It is believed, that this is the case when using zinc catalysts in lubricants.

To inert solvents used in the above reaction can be, giiör en hydrocarbon oils, e.g. mineral oil, Kerosene, neutral mineral oils, xylene, halogenated hydrocarbons

809831/068 »

substances, e.g. carbon tetrachloride, dichlorobenzene, tetrahydrofuran, etc.

Metal salts that can be used as catalysts in the invention include carboxylic acid salts of Zn, Co, Mn and I "e. Metal catalysts, which are based on strong acids (HCl, Sulphonic acid, HpS (K, ENT ,, etc) and bases tend to be derived to reduce the yield of the oxazoline products in favor of imide or ester formation. For this reason, Catalysts Strong acids or basic catalysts are not preferred and generally avoided. To the manufacture The carboxylic acids used of the desired catalysts include C- to C-g, e.g., C-C to C-g acids, such as the saturated ones or unsaturated mono- or dicarboxylic aliphatic hydrocarbon acids, especially fatty acids. Specific examples of such desired carboxylic acid salts include Zinc acetate, zinc formate, zinc propionate, zinc stearate, manganese acetate (Manganese II acetate), iron tartrate, cobalt acetate (cobalt II acetate), etc. Termination of the oxazoline reaction can be easily accomplished using periodic infrared spectral analyzes take place, using for oxazoline formation (C = N absorption band at 6.0 / µm) until a maximum in with respect to lactone absorption or water formation stops.

Boron compounds which are suitable in the reaction with the oil-soluble mono- and bis-oxazolines and the lactone oxazolines include boron oxide, boron oxide hydrate, acids of boron such as boronic acid / eg alkyl-B (OH) ₂ or aryl-B (OH) ) ₂ 7 and boric acids,

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preferably H ^ BO, and the esters of these acids of boron.

Typical examples of boronic acids include methyl boronic acid, Phenyl boronic acid, cyclohexyl boronic acid, p-heptyl phenyl boronic acid and dodecylboronic acid.

The boric acid esters include mono-, di- and tri-substituted ones organic esters of boric acid with alcohols or phenols such as butanol, octanol, cyclohexanol, cyclopentanol, Ethylene glycol, 1,3-butanediol, 2,4-hexanediol, polyisobutene substituted phenols. Lower alcohols, 1,2-glycols and 1,3-glycols, i.e., those with less than about 8 carbon atoms are particularly useful in making the boric acid esters for the Suitable for purposes of this invention. Processes for the preparation of the esters of acids of boron are known and in the literature (see "Chemical Reviews", pp. 959-1064, volume 56).

The general method for formation of öllösliohem borated oxazolines ".the invention by reacting the Oxazolinmaterials with the boron-containing compound is usually carried out in such a manner that a mixture of the reactants at a temperature above about 60 ⁰ C, preferably in the range of about 80 ⁰ C to about 200 ⁰ C heated. However, when boric acid or oxide is used, the process can be carried out at lower temperatures (such as 60 C Ue 100 C), preferably at about 80 C. The. Use of a solvent such as benzene, toluene, gasoline, mineral oil, xylene, η-hexane or

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the like are often desirable in the above process for control of the reaction temperature and removal to facilitate the use of water »Mineral oil is preferred to facilitate the use of the products as a lubricating oil additive.

The oil-soluble oxazolines react readily with the boron compounds, for example boric acid, at these slightly elevated temperatures to form the boron esters of the invention. When the substituted oxazoline has two available hydroxyl groups in the reaction, as with the ilono-oxazoline, the oxazoline can be reacted with the boron compound in a molar ratio of 1: 1 or 1: 2. If water of reaction is formed in the course of the reaction as with the preferred boric acid, it is necessary to remove all or part of the water from the reaction mixture, for which purpose it is separated off overhead, either by purging with an inert gas such as nitrogen or by simple azeotropes Distillation, keeping the temperature below 10O ⁰ C in order to avoid the destruction of the oxazoline ring.

Useful oxazoline materials according to the invention retain oxazoline absorption bands at 6.0-6.1 / µm at a level which corresponds at least to the carbonyl absorption band at 5.9 / µm which is obviously attributable to the imide degradation products. It is preferred that the absorption band at 6.0-6.1 / µm be 25 ° greater than that at 5.9 / µm.

If one uses a transesterification to get boron instead of the hy-

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To use hydroxy groups, the reaction temperature and time can be controlled in such a way as to avoid excessive gelation of the product.

The boronization of the oxazoline materials should be carried out so that about 0.1 to 2.0 wt. $, Preferably 0.2 to 1 wt. $ Boron is present based on the weight of the material.

For use as borated oxazoline additives in lubricating oil formulations For example, the oil-soluble borated oxazoline reaction products of the invention can typically be in a wide variety are introduced by lubricating oil preparations, such as in engine lubricating oils, automatic transmission fluids, etc., at concentrations generally in the range of about 0.01 to 20 wt%, e.g., 0.1 to 10 wt%, preferably 0.3 to 3.0 wt. #, Based on the total preparation. To lubricants, to which the lactone oxazoline products may be added include not only the hydrocarbon oils derived from petroleum, but also synthetic ones Lubricating oils such as polyethylene oils, alkyl esters of dicarboxylic acids, complex esters of dicarboxylic acids, polyglycol and alcohol, Alkyl esters of carboxylic or phosphoric acids, polysilicones, Fluorocarbon oils, mixtures of mineral lubricating oils and synthetic oils in all proportions, etc.

When using the products of this invention as multifunctional additives with detergent and anti-rust properties in petroleum fuels such as gasoline, kerosene, diesel fuels, heating oil No. 2 and

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Other middle distillates are used, a concentration of the additive in the fuel will usually be in the range from 0.001 to 0.5% by weight, based on the weight of the total preparation, be used.

The additive can expediently be sold as a concentrate containing a smaller proportion of additive, e.g. 20 to 90 parts by weight, dissolved in a larger proportion of mineral lubricating oil, e.g., 10 to 80 parts by weight, other additives may be present.

Other conventional additives may be present in the aforesaid formulations or concentrates, including Colorants, pour point depressants, anti-abrasive agents such as tricresyl phosphate or zinc dialkyldithiophosphates with 3 to 8 Carbon atoms in each alkyl group, antioxidants such as N-phenyl-oc-naphthylamine, tert-octylphenol sulfide, 4,4'-methylene-bis (2,6-di-tert-butylphenol), Viscosity index improvers, such as ethylene-propylene copolymers, polymethacrylates, Polyisobutylene, alkyl fumarate-vinyl acetate copolymers and the like, de-emulsifying agents such as polysiloxanes, ethoxylated Polymers and the like.

The invention is described in further detail in the following examples which illustrate the preferred embodiments of the invention.

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example 1

Boron-containing bis-oxazoline of polyisobutenylsuccinic anhydride

The polyisobutenylsuccinic anhydride bisoxazoline is obtained by reacting one mole of polyisobutenyl (S _n 980) succinic anhydride with a saponification number of 80 with two moles of tris (hydroxymethylamino) methane in accordance with the teachings of German DOS 2512201.

A solution of 900 g of polyisobutenylsuccinic anhydride bis-oxazoline in 900 g of Solvent 15ON mineral oil is placed in a S-liter ^ neck reaction flask. The solution was sparged overnight at 80 ⁰ O with nitrogen and gives 148 g of tributyl borate (4.7 wt $,., Boron) to. The mixture is kept at! Temperatures of 13O ⁰ O ⁰ O to 16O reflux for 1 hour, after which the temperature is maintained for 5 hours at about 200 ⁰ C. It is then bubbled through the reaction mixture with nitrogen for an additional hour at about 200 ⁰ C. The product is a dark viscous oily solution containing about 50 percent active ingredient $} analysis:... ^ 0.32 percent boron and 0.92 wt # Nitrogen. The infrared absorption curve shows no significant loss of the oxazoline structure (substantial absorption at 6 µm).

Example 2

Boron-containing monooxazoline of polyisobutylene succinic anhydride

(2A) 200 g (approx. 0.1 mol) of a 51 to 53 # igen are mixed Solution of PolyiBobutenylsuccinic anhydride (PIBSA with an (S ^ value of 960 and a desulfurization number of 84) in

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Solvent 150 neutral oil with 0.1 mol (12.1 g) tris (hydroxymethyl) aminomethane (THAM) and 0.1 g zinc acetate. The mixture is heated then the G-emisch8bis 10 hours at 200 ⁰ C, is distilled off until all the water and the infrared spectrum prevailing ester carbonyl and 0xazolin (C = N) absorption bands at 5.75 and 6.03 / um shows how this for a monooxazoline product is to be expected. After stripping, the product is filtered hot through a Celite 505 filter cake. That
When analyzed, the filtrate has 0.69% by weight nitrogen (Kjeldahl).

(2B) are mixed 165 g (0.05 mole) of 50 $ strength by weight oil solution, prepared as described above with 0.05 mole (33 g), boric acid and gradually heated to 100 ⁰ C. The infrared spectrum shows a half hour at 80 ⁰ C the disappearance of the typical absorption bands (3> 0 and 9.6 / µm) which can be ascribed to the oxazoline reactant. It is then bubbled through the Reaktionaprodukt one hour at 100 ⁰ C with nitrogen, the reaction to remove water. The infrared spectrum of the final product shows a strong oxazoline absorption band at 6.03 / µm which substantially exceeds the strength of the absorption band at 5 »87 / µm (which is attributable to the carbonyl absorption of the imide products). The analysis of the 50% strength by weight oil solution of the boron-containing monooxazoline, prepared as above, shows 0.69% by weight of nitrogen (Kjeldahl) and 0.4% by weight of boron.

Example 3

Borated bis-oxazoline from polyisobutenyl (ß 1300) succinic anhydride

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500 g (0.459 mol) of a (PIBSA) with a content of about 90 carbon atoms and a saponification number of 103 are diluted with 557 g of Solvent 150 neutral. The mixture is heated with stirring under a nitrogen blanket to 177 ⁰ G, giving 265 g (0.87 mol) of a 40 $ aqueous solution (IHAM) -Lb "solution and 3.4 g of zinc acetate (in solution) was added dropwise to 2 hours The reaction temperature is maintained at 177 ° C. while bubbling through during the addition in order to facilitate the removal of the water vapor After the addition has ended, the reaction mixture is stripped off with nitrogen at 177 ° C. for 10 hours and then filtered.

(3B) 3000 g FiItrat (about 1.0 mole bis-oxazoline), prepared as described previously, is mixed with 53.5 g of boric acid and gradually heated to 100 ⁰ C. When the temperature reaches 100 ⁰ G, shows the Infrared analysis of the reaction mixture shows that the absorption bands at 3.0 and 9.6 / µm have completely disappeared, from which one can recognize the end of the boronization. It bubbled through the reaction mixture at 100 to 110 ⁰ O 1 h with nitrogen to remove any water present to which, and then filtered.

The filtrate, which contains the boron-containing bis-oxazoline product, has infrared absorption bands in the range from 5 »8 to 6.1 / µm, which are essentially unchanged compared to the bands, obtained for the bis-oxazoline product of 3 (A), thereby maintaining the oxazoline structure in the boron-containing Can recognize derivative. The absorption at 6.03 / µm

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if the absorption increases significantly at 5 »87 / µm. The Piltrat when analyzed, it has 1.15% by weight nitrogen and 0.29% by weight boron.

Example 4

Borated bis-oxazoline from polyisobutenyl (EL 960) succinic acid anhydride

(A) 200 g (approx. 0.1 mol) of a 51% by weight solution of polyisobutenylsuccinic anhydride (PIBSA) of (fl} »960 with a saponification number (SAP) of & £ J in solvent 150 neutral are heated up about 100 to 120 ⁰ C. is then added 0.2 mole (24.2 g) tris (hydroxymethyl) aminomethane (THAM), and 0.1 g of zinc acetate to the mixture is heated to 180 ° -185 ⁰ C to the. The formation of water ceases (after about 2 hours). The oxazoline (C = N) infrared absorption band of the product is at its maximum at this point in time. The product is then filtered.

(B) 200 g of the product filtrate from 4 (A) 0.1 mol of bis-oxazoline) are mixed with 6.2 g (0.1 mol) of boric acid and heated to 100 ^° C. and this temperature is maintained for 1 hour. The infrared analysis shows the disappearance of the characteristic absorption band of 3 »0 and 3.6 / µm, from which it can be seen that the formation of borate ester has ended. The reaction mixture is then bubbled with nitrogen. The piltrate containing the borated bis-oxazoline product has infrared absorption bands in the 5-8 to 6.1 / µm region which are essentially unchanged from the bis-oxazoline product of 4 (A), from which the oxazoline structure Retained in the borated derivative of Example (4B) . The absorption at 6.03 / µm significantly exceeds the absorption at 5.87 / µm. Analysis of the filtrate

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1.2 wt. $ Nitrogen and 0.478 wt. $ Boron.

Example 5

Reaction product of Polybutenylbernsteinsaureanhydrid, tris- (Hydrox; vTnethyl) aminomethane and boric acid This example is a repeat of Example 3 of German Patent Application DOS 2,534,922 \ Disclosed 02.26.1976.

A mixture of 100 g (0.05 mol) of polybutenylsuccinic anhydride, prepared from a polybutene having about 130 carbon atoms and maleic anhydride in the presence of t-butyl peroxide, and 6.05 g (0.05 mol) of tris (hydroxylmethyl) - is added aminomethane in a suitable reaction vessel. The mixture is heated to about 175 ^° C. with stirring and is kept at this temperature until no further formation of water occurs. The mixture is cooled to 75 ^° C. and 3.5 g (0.057 mol) of boric acid together with 15 g (0.2 mol) of butanol are added. It then holds the reaction mixture to about 225 ⁰ C for 10 hours under reflux. The reaction product is filtered and refluxed under reduced pressure at 165 ° C., whereby a viscous liquid end product is obtained which is diluted to a content of about 52% by weight of active ingredient with solvent 15ON mineral oil. Analysis of the diluted solution shows 0.237 wt. $ Boron and 0.31 wt. $ Nitrogen (Kjeldahl). Infrared analysis shows intense absorption bands at 5.87 µm (attributable to the imide products). In sharp contrast to this, the oxazoline absorption band at 6.03 / µm has essentially disappeared

809831/0681

Example 6 Borated polyisobutyl lactone oxazoline

(A) 600 g of a solution of Solvent 150 neutral oil with a content of 51% by weight of polybutenylsuccinic anhydride (PIBSA (β _n ~ 960, saponification number 84) are mixed with 6 g of water and 20 g of Amberlyst 15 catalyst mixture at 10O ⁰ C for about 8 to 10 hours and then for 2 hours at 13O ⁰ C. the infrared analysis shows the presence of strong absorption bands in the range of about 6.5 to 8.5 / um, which are typical for Laktonsäuren. dilute the product with hexane, filtered and treated for 4 hours on the rotary evaporator at 80 to 100 ⁰ C. the residue is after treatment with diethylamine in excess an infrared spectrum with a strong Laktoncarbonylabsorptionsbande at 5 _f 64 / um.

(B) Mix 200 g (about 0.1 mol of polyisobutyllactonic acid) of the product solution, as described above in Example 6A, and 12.1 g (0.1 mol) of (THAM) in a reaction flask and heat gradually for 1 to 1 1/2 hour to about 180 to 185 ° C. The product was diluted in 200 ml of hexane, filtered and treated there at 90 ⁰ C for 2 hours on the rotary evaporator. The infrared analysis of the product solution, which contains about 50% by weight of polyisobutyllactone oxazoline, shows strong absorption bands at 5 | 65 to 6.0 μm, which are attributable to the lactone oxazoline functionality. The analysis of the solution of this product shows 0.69% by weight of nitrogen (Kjeldahl) (theoretical Ιΐ 0.67 $>} .

(C) 200 g of polyisobutyl lactone oxazoline solution (0.1 mol

809831/0688

Laktonoxazolin) as described above in Example 6 (B) "to 120 ⁰ C. and 0.1 mol (6.2 g) boric acid added portionwise over 15 minutes. It was bubbled through the mixture with nitrogen while 1 hour at 150 ⁰ C. The infrared analysis of the product solution shows the disappearance of the absorption bands at 3 »0 and 9» 6 / µm, which are typical for the oxazoline reactants. The spectrum also shows the lactone carbonyl and oxazoline (C = N Absorption bands at 5.7 and 6.03 / µm. This product solution, which contains about 50% by weight of borated product, when analyzed shows 0.69% by weight of nitrogen (Kjeldahl) and 0.49% by weight of boron.

Example 7

Borated bis-oxazoline of polyisobutenyl- (SL 1300 ^ amber acid anhydride

In this example, tributyl borate is used as a boron compound such as used in Example 1, although in this case the product was very highly viscous.

A polyisobutenyl-bis-oxazoline is produced from Polyisobutenyl succinic anhydride having about 90 carbon atoms and a saponification number of 103 with solvent oil a nitrogen value of 1 wt. Bubbled through 350 g of this material at 125 ° C for 1 hour with nitrogen to the To remove traces of water and boiling tails. Give 30 g (0.13 mol) tributyl borate and equips the reaction flask with a (cold finger) condenser for overhead collection. as Temperatures are used at 160 0 for 1 hour and a second

809831/0681

Hour at 17O ⁰ C, 3 1/2 hours at 180 ⁰ C and then purged with nitrogen for 1 1/2 hours at 200 ⁰ C. The pot collected material has a weight of 27 g, mainly butanol. The product contains 1.03 wt. ^ Nitrogen and 0.399 Gew.?£ Bor. It is a dark brown gel-like material having a Saybolt TJniversal viscosity at 21O ⁰ F of 5643 seconds, an increase of more than $ 400>. The bis-oxazoline used as the starting material had a viscosity at 210 ^° J of 1371 seconds.

Example 8

Hochtemperaturborierung up-oxazolines of polyisobutenyl succinic anhydride

The following examples, in which the boration with boric acid is conducted at about 200 ⁰ C (225 ° C, the condition of Example 3 of DOS 2,534,922, this being the Borierungstemperatur of Example 5) show that a substantial amount of oxazolines in the PIBSA-bis-oxazoline can be converted into products of the imide type, as can be seen by infrared analysis.

(A) is mixed 165 g of an oil solution of polybutenyl (M 96O) -bis-oxazoline (0.05 mol, 50 wt. # Ai) with 0.05 mole (3.3 g) boric acid, and heated for 8 hours at 200 ⁰ C. After a temperature of 20O ⁰ C has been reached, the infrared spectrum shows the absence of the absorption band of 9 »6 / μm, but the intensity of the oxazoline band becomes weaker and the strength of the imide absorption band at 5.9 / μm increases. At the end of the 8 hour heating period, the infrared spectrum of the product shows a

809831/0681

intense imide absorption band at 5.9 / µm and indeed no Oxazolina "absorption in the range of 6.0 to 6.1 / µm. The Product solution (50% by weight) shows 1.06% by weight when analyzed (Kgeldahl) and 0.37 wt. # Boron.

(B) 300 g (0.1 mol, 50 $> ai) of polyisobutenyl-bisoxazoline, prepared as in Example 3 (A), are mixed with 6.4 g of boric acid and heated to 200 ^° C. for 7 to 8 hours. The infrared analysis of this Reaction mixtures show a substantial decrease in the intensity of the oxazoline band at 6.03 / µm. At the end of the heating period (10 hours), the IR analysis shows that the oxazoline band has completely disappeared} the product obtained gives a gel-like material after cooling. The analysis of this gel (50% by weight) shows 1.13% by weight of SN (Kjjeldahl) and 0.44% by weight of boron.

Example 9

Sludge Inhibition Laboratory Tests (SIB) The products of Examples 2, 3, 4 and 5 are subjected to a Sludge Inhibition Bench (SIB) -iDest ' ^1. This has been determined after a large number of evaluations excellent investigation for determining the dispersing power of Sohmierolto dispersing additives.

The selected medium in the Sludge Inhibition Bench Test is a used engine mineral lubricating oil with an initial viscosity of about 325 STJS at 10O ⁰ I ¹ , the preceding

809831/088 «

was used in a taxi, which generally travels short distances, creating a high concentration of mud precursors are formed. The oil that was used contains only one refined base mineral lubricating oil, one Viscosity index improver, a pour point depressant and a zinc dialkyldithiophosphate anti-abrasion additive. The oil contained no sludge dispersants. This used oil was obtained by getting out of the oil pan of the taxi in Takes oil and refills at 1000 to 2000 mile intervals.

The sludge inhibition laboratory test is carried out in the following manner. The engine oil used as previously described, milky brown in color, is freed of sludge by centrifuging it for half an hour at about 39,000 gs. The clear-light red supernatant oil obtained is then decanted from the insoluble sludge particles, whereby these are separated off. However, it also contains this supernatant oil-soluble sludge precursors which, when heated under the conditions used in this experiment, tend to form further oil-insoluble sludge deposits. The sludge inhibition properties of the additives to be investigated are determined by adding to portions of the supernatant oil used a small amount, such as 0.5% by weight, based on the active ingredient base, of the particular additive to be investigated. 10 g of each mixture are then placed in a tubular center

809831 / 0G88

trifuge alii given stainless St and "at 28O ⁰ F (137 ° C) for 16 hours in the presence of air. After heating, the tube containing the upcoming for investigating oil is cooled, and then a 30-minute Zentrifugentehandlung is at approximately 39,000 gs. Any new sludge deposits that form in this stage are separated from the oil by decanting the supernatant oil and the sludge deposits are then carefully washed with 15 ml of pentane to remove any remaining oil from the sludge « The weight of the new solid sludge formed in the test is then determined in mg, for which purpose the residue is dried and weighed, and the results are given as mg of sludge per 10 g of oil, with differences as small as 1 part per 10,000 Parts can be measured. The less new sludge is formed, the more effective the additive is as a sludge dispersant. In other words, when the additive is effective, at least a portion of the new sludge, which forms on heating and oxidation, is suspended in the oil so stably that it is not precipitated during centrifugation.

Using the study described above, one compares the dispersing effects of the borated oxazolines with the present one Invention with the corresponding non-borated oxazolines, the borated imide-containing product of DOS 2534922 and a commercially available dispersant identified as PIBSA-TEPA. The PIBSA-TEPA dispersant

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is prepared by reacting 1 mole of tetraethylenepentamine with 1.5 moles Polyisobuteny! anhydride (saponification value 80), there is obtained from polyisobutylene I _n IOOO the latter. The PIBSA-TEPA dispersant, used in the form of an additive concentrate, has about 50% by weight of # PIBSA / TEPA in 50% by weight of mineral lubricating oil. This PIBSA / TEPA additive concentrate, when analyzed, has about 1.8 $ nitrogen, which indicates that the active ingredient, ie, PIBSA / TEPA as such, contains about 3.6 <$> nitrogen. The test results are given in the table below.

Table I.
Results of the investigation of the sludge dispersibility

Additive of
example Mg sludge / 10 g Oil at
0.5 Grew. # 2A 0.69 2.58 2 B 0.69 4.36 3A 1.13 0.94 3B 1.13 3.69 4A 1.2 5.6 4B 1.2 2.93 5 0.31 8.84 without - 10.0 PIBSA / TEPA 0.60 7.78 Example 10 Evaluation of the products at a
investigation Paint formation inhibition

Each test sample consists of 10 g of soothing oil, which is 0.07 g

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Additive concentrate (50% active ingredient) contains »from which it follows that a total content of 0.35% by weight of additive is present in the test sample. The oil to be tested, in which the additive is mixed, is a commercially available lubricating oil (9.93 g) »which can be obtained from a taxi after driving 2,000 miles with the lubricating oil. Each 10 g sample is treated overnight in the heat at about 140 ^° C. and then centrifuged in order to remove the sludge. The supernatant liquid of each sample is subjected to cyclical heat treatments from about 150 ^° C. to room temperature for a period of 3 »5 hours at a frequency of about 2 cycles / min. During the heating phase, grass containing a mixture of about 0.7 vol- £ SO ₂ , 1.4 vol- # HO and the remainder air is bubbled through, and during the cooling phase water vapor is bubbled through the test samples. After the end of the test period, and the test sequence can be repeated if necessary to determine the inhibiting effect of any additive , the wall surfaces of the test flasks in which the samples are contained are visually assessed for paint inhibition. The amount of laoc deposited on the walls is rated with values from 1 to 7, with the higher number indicating the greater amount of varnish. It was found that these tests correspond to the lao results obtained as a result of an "MS-YC engine" test. The results, which are summarized in Table II, indicate that the boron-containing oxazoline reaction products of this invention have superior varnish inhibition efficacy over the non-borated counterparts and the product of

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KOS 2534922.

Table II Ot35 Gewo $ additive added to the IT investigation oil

Additive from VIB assessment example

Investigative
sample borated 1 no 2 there 3 no 4th there 5 no 6th there 7th there 8th no 9 no

2A 6th 2 B VJI 3A VJl 3B 4th 4A VJ) 4B 4th VJl 7th Blank sample 11 PIBSA / TEPA 7th

The values in Table II illustrate the excellent laokinhibierungswirlcsamlceit the borated Additivirodulcte the invention, especially when compared to a known commercially available dispersant which is referred to as FIBSA-TBPA, and opposite a borated dispersant, as described in the DOS application 2534922 is.

Patient

809831/0681

Claims (1)

Patent claims: 1 .. oil-soluble boron-containing oxazoline material with a content from about 0.1 to 2.0 wt. $ boron, with one or two oxazoline rings and a substantially saturated hydrocarbon group containing at least about 50 carbon atoms. 2. oxazoline material according to claim 1, characterized in that the material is a derivative of an oxazoline reaction product of a substantially saturated aliphatic hydrocarbon-substituted C ₁ -C 1 Q saturated dicarboxylic acid material, wherein the hydrocarbon group has a number average molecular weight of about 700 to about 140,000, and about 1 to about 2 molar equivalents, per molar equivalent of dicarboxylic acid material, of a 2,2-disubstituted-2-amino-1-alkanol having 2 to 3 hydroxy groups and a total content of 4 to 8 carbon atoms, the alkanol having the general formula below NH ₂ - G - OH ₂ OH, where X is an alkyl or hydroxyalkyl group and at least one of the X substituents is a hydroxyalkyl group of the general formula - (CH ₂ ) OH, where η is 1 to 3, and 809831/0688 ORIGINAL! HSPECTED that this is then condensed with a boron oxide. 5. Oxazoline material according to one of claims 1 or 2, characterized in that it is by reacting a molar fraction of an alkenyl succinic anhydride or the acid at about 1.5 to about 2 molar parts Alkanol received. 4. oxazoline material according to any one of claims 1 to 3, characterized in that the dicarboxylic acid material was reacted with the alkanol at a temperature of about 14O ⁰ C to 240 ⁰ C for 1/2 to 24 hours, whereby at least one carboxylic acid group is converted into an oxazoline ring and that the reaction product is borated by condensation with boron oxide, acids of boron or esters of acids of boron in an amount that is about 0.1 to 2.0 grains. $ boron, based on the total content of the borated ester derivative, available. 5. oxazoline material according to any one of claims 1-4, characterized in that the borated material is the bis-oxazoline product of hydrocarbon-substituted succinic anhydride which is reacted with about two molar equivalents of tris-hydroxymethylaminomethane, the bis-oxazoline condensing was with boric acid at a temperature of about 80 to 120 ⁰ C, and an infrared absorption at 6.03 / µm, which significantly exceeds the infrared absorption at 5.87 / µm. 809831 / O6Ö0 6. Oxazolinmaterial according to any one of claims 1 'to 5, characterized in that it has received disubstituierten- 2,2-by combining heating a Molaranteils a ^C 4 ~ ^C 400 ° ^k k ^ ^{lenwassers off} ~ ^su kstituierten laktonsäurematerials with a molar fraction of a 2-Amino-1-alkanol with 1 "to 3 hydroxyl groups and a total content of 4" to 8 carbon atoms at a temperature of 100 to 240 0 until the formation of water ceases, whereby the termination of the oxazoline reaction is indicated, and that then this product with Boron oxide, boric acids or esters of acids of boron has been condensed in an amount such that about 0.1 to 2 wt. $ Boron, based on the total weight of the borated reaction product, is present. 7. Preparation according to one of claims 1-4, characterized in that the borated Oxazoline reaction product is the mono-oxazoline product of an alkenyl succinic anhydride or acid that is which one with about one molar equivalent of tris-hydroxymethylaminomethane has implemented, the alkenyl substituent being a Number average molecular weight in the range of about 1000 to about 20,000. 8. lubricant preparation, characterized in that it contains a larger amount of lubricating oil and a small but dispersing amount of dispersing and lacquer formation-inhibiting oil-soluble borated oxazoline material according to any one of claims 1 to 7. 809831/0688 9. lubricating oil preparation, characterized in that it contains a larger amount of lubricating oil and 0.01 to 20 wt. Oil-soluble, borated oxazoline or borated Lactonoxazoline reaction product according to any one of claims 1 to 8 contains. 10. Preparation according to one of claims 8 or 9 »characterized in that the oil-soluble The derivative of the reaction product is from 1 to 2 moles of boric acid with a molar proportion of a bis-oxazoline product obtained from the reaction of this Aikenylsuccinic anhydride with about has received two molar equivalents of tris-hydroxymethylaminomethane, 11. Preparation according to one of claims 8 to 10, characterized in that the borated oxazoline reaction product is the mono-oxazoline product of hydrocarbon-substituted succinic anhydride which has been reacted with about 1 molar equivalent of tris-hydroxymethylaminomethane, the mono-oxazoline being reacted further with an amine which is an alkylene polyamine having 2 to 12 nitrogen atoms, in which the pairs of nitrogen atoms are linked by alkylene groups having 2 to 4 carbon atoms and which was then condensed ^{with boric acid at a temperature in the range from about 80 to 100 0 O.} 12. Process for the preparation of an oil-soluble borated Oxazoline material, characterized in that that a ^ cq '^ io 000 hydrocarbon substitute 509831/0588 - 3t) - tes oxazoline material with a boron compound, namely boron oxide, acids of boron and / or esters of acids of boron in an amount such that there is about 0.1 to 2 wt. $ boron, based on the total weight of the borated reaction product, at a temperature above condensed about 60 0 for at least a time sufficient for the reaction product to have no infrared absorption at 3 »0 and 9» 6 / µm, provided that when boric acid or boron oxide is used, the temperature used is in the range of 60 to 100 ⁰ O is. 109831/0611